Cover -- Title page -- Copyright page -- Contents -- Preface -- List of Abbreviations -- 1: Introduction -- 1.1 Why Study Organometallic Chemistry? -- 1.2 Coordination Chemistry -- 1.3 Werner Complexes -- Stereochemistry -- Chelate Effect -- Werner's Coordination Theory -- 1.4 The Trans Effect -- 1.5 Soft versus Hard Ligands -- 1.6 The Crystal Field -- High Spin versus Low Spin -- Inert versus Labile Coordination -- Jahn-Teller Distortion -- Low- versus High-Field Ligands -- Magnetism and Nuclearity -- Other Geometries -- Isoconfigurational Ions -- 1.7 The Ligand Field -- 1.8 The sdn Model and Hypervalency -- 1.9 Back Bonding -- Frontier Orbitals -- π-Donor Ligands -- 1.10 Electroneutrality -- Oxidation State Trends -- Periodic Trends -- 1.11 Types of Ligand -- Ambidentate Ligands -- Actor and Spectator Ligands -- Multifunctional Ligands29 -- Organometallic versus Coordination Compounds -- References -- Problems -- 2: Making Sense of Organometallic Complexes -- 2.1 The 18-Electron Rule -- Covalent Electron Counting Model -- Ionic Electron Counting Model -- Electron Counts for Common Ligands and Hapticity -- Bridging Ligands -- Zero-Electron Ligands -- 2.2 Limitations of The 18-Electron Rule -- Steric Stabilization of Reactive Species -- 2.3 Electron Counting in Reactions -- 2.4 Oxidation State -- Oxidation State versus Real Charge -- Ambiguous Oxidation States and Noninnocent Ligands -- Maximum and Minimum Oxidation States -- Net Ionic Charge -- 2.5 Coordination Number and Geometry -- 2.6 Effects of Complexation -- Ligand Polarization -- Free ≠ Bound -- Symbiotic and Antisymbiotic Effects -- 2.7 Differences between Metals -- Real Charge -- References -- Problems -- 3: Alkyls and Hydrides -- 3.1 Alkyls and Aryls -- Metal Alkyls as Stabilized Carbanions -- β Elimination -- Stable Alkyls -- Agostic Alkyls -- β Elimination of Other Groups.

Reductive Elimination -- Kinetic Stability from Bulky Substituents -- Preparation of Metal Alkyls -- Cyclometalation -- Oxidative Addition -- Insertion -- Bridging Alkyls -- Metalacycles -- η1 and η2-Acyl and Vinyls -- 3.2 Other σ-Bonded Ligands -- Group 14 Elements -- Groups 15-17 -- Oxophilicity and Functional Group Tolerance -- 3.3 Metal Hydrides -- Characterization -- Synthesis -- Reactions -- Hydricity -- Bridging Hydrides -- 3.4 Sigma Complexes -- Dihydrogen Complexes20 -- Characterization -- Reactions -- Agostic Species -- 3.5 Bond Strengths -- Supramolecular Interactions -- References -- Problems -- 4: Carbonyls, Phosphines, and Substitution -- 4.1 Metal Carbonyls -- Preparation of Carbonyls -- Reactions of Carbonyls -- Bridging Carbonyls -- Isonitriles -- Thiocarbonyls -- Nitrosyls -- Cyanide -- Other CO Analogs -- 4.2 Phosphines -- Structure and Bonding -- Tolman Electronic Parameter and Cone Angle -- Bite Angle -- 4.3 N-Heterocyclic Carbenes (NHCs) -- 4.4 Dissociative Substitution -- Kinetics -- Stereochemistry and Trans Effect -- Electronic and Steric Factors -- 4.5 Associative Substitution -- Kinetics -- Trans Effect -- Solvent Participation -- Ligand Rearrangements -- 4.6 Redox Effects and Interchange Substitution -- 17e and 19e Species -- The Interchange Mechanism -- 4.7 Photochemical Substitution -- Carbonyls -- Other Photochemical Processes -- 4.8 Counterions and Solvents in Substitution -- "Noncoordinating" Anions -- References -- Problems -- 5: Pi-Complexes -- 5.1 Alkene and Alkyne Complexes -- Synthesis -- Reactions -- Alkyne Complexes -- 5.2 Allyls -- Synthesis -- Reactions -- Related Ligands -- 5.3 Diene Complexes -- Cyclobutadiene Complexes -- Trimethylenemethane -- 5.4 Cyclopentadienyl Complexes -- Bent Metallocenes -- Synthesis -- Cp Analogs -- 5.5 Arenes and Other Alicyclic Ligands -- Synthesis -- Other Arene Ligands.

η7 Ligands -- η8 Ligands -- 5.6 Isolobal Replacement and Metalacycles -- 5.7 Stability of Polyene and Polyenyl Complexes -- References -- Problems -- 6: Oxidative Addition and Reductive Elimination -- 6.1 Introduction -- 6.2 Concerted Additions -- 6.3 SN2 Pathways -- 6.4 Radical Mechanisms -- 6.5 Ionic Mechanisms -- 6.6 Reductive Elimination -- Octahedral Complexes -- Other Complexes -- Binuclear Reductive Elimination -- Reductive Elimination of C-F, -O, and -N -- 6.7 σ-Bond Metathesis -- 6.8 Oxidative Coupling and Reductive Fragmentation -- References -- Problems -- 7: Insertion and Elimination -- 7.1 Introduction -- 7.2 CO Insertion -- Enhancing Insertion Rates -- Apparent Insertions -- Double Insertion -- 7.3 Alkene Insertion -- Regiochemistry of Insertion -- Syn versus Apparent Anti Insertion -- Insertion into M-H versus M-R -- Radical Pathways -- Alternating CO/Alkene Insertion -- 7.4 Outer Sphere Insertions -- 7.5 α, β, γ, And δ Elimination -- β Elimination -- α Elimination -- Other Eliminations -- References -- Problems -- 8: Addition and Abstraction -- 8.1 Introduction -- 8.2 Nucleophilic Addition to CO -- 8.3 Nucleophilic Addition to Polyenes and Polyenyls -- Davies-Green-Mingos Rules -- Wacker Process -- Alkyne Hydration -- 8.4 Nucleophilic Abstraction in Hydrides, Alkyls, and Acyls -- Hydrides -- Alkyls and Acyls -- 8.5 Electrophilic Addition and Abstraction -- Addition to the Metal -- Addition to a Metal-Ligand Bond -- Addition to Ligand -- Abstraction of Alkyl Groups -- 8.6 Single-Electron Transfer and Radical Reactions -- References -- Problems -- 9: Homogeneous Catalysis -- 9.1 Catalytic Cycles -- Homogeneity -- Thermodynamics -- Kinetics -- Mechanism, Intermediates, and Kinetic Competence -- Cooperative Catalysis -- Deactivation -- Choice of Metal and Ligands -- 9.2 Alkene Isomerization -- Alkyl Mechanism -- Allyl Mechanism.

9.3 Hydrogenation -- Oxidative Addition Pathway -- Directing Effects -- Asymmetric Catalysis -- Reversibility -- Heterolytic H2 Activation -- Homolytic H2 Activation -- Outer Sphere Hydrogenation -- Transfer Hydrogenation -- Nanoparticles -- 9.4 Alkene Hydroformylation -- Chelating and Phosphite Ligands -- 9.5 Alkene Hydrocyanation -- 9.6 Alkene Hydrosilylation and Hydroboration -- Hydrosilylation -- Hydroboration -- 9.7 Coupling Reactions -- 9.8 Organometallic Oxidation Catalysis -- Oxidase Reactions -- Water Splitting and C-H Oxidation -- 9.9 Surface, Supported, and Cooperative Catalysis -- Surface Organometallic Chemistry -- Cooperative Catalysis -- Hidden Acid Catalysis -- References -- Problems -- 10: Physical Methods -- 10.1 Isolation -- 10.2 1H NMR Spectroscopy -- Virtual Coupling -- Diastereotopy -- Chemical Shifts -- Paramagnetic NMR -- 10.3 13C NMR Spectroscopy -- 10.4 31P NMR Spectroscopy -- Mechanistic Study of Wilkinson Hydrogenation -- 10.5 Dynamic NMR -- Rate of Fluxionality -- Ligand Fluxionality -- 10.6 Spin Saturation Transfer -- 10.7 T1 and the Nuclear Overhauser Effect -- T1 and H2 Complexes -- PHIP and SABRE -- Nuclear Overhauser Effect -- 10.8 IR Spectroscopy -- Carbonyls -- Other Ligands -- Band Identification by Isotope Substitution -- Raman Spectroscopy -- 10.9 Crystallography -- Limitations -- 10.10 Electrochemistry and EPR -- 10.11 Computation -- 10.12 Other Methods -- Mass Spectroscopy -- Single-Molecule Imaging -- Interpretation of Results -- References -- Problems -- 11: M-L Multiple Bonds -- 11.1 Carbenes -- Fischer versus Schrock Carbenes -- Fischer Carbenes -- Schrock Carbenes -- Intermediate Cases -- Boryls -- 11.2 Carbynes -- Synthesis -- Structure and Spectra -- Reactions -- 11.3 Bridging Carbenes and Carbynes -- Structure and Spectra -- Reactions -- 11.4 N-Heterocyclic Carbenes -- Synthesis of NHC Complexes.

Polydentate NHCs -- Applications -- 11.5 Multiple Bonds to Heteroatoms -- Oxo Wall -- Synthesis -- Spectra and Structure -- References -- Problems -- 12: Applications -- 12.1 Alkene Metathesis -- Mechanism -- Selectivity in Cross Metathesis -- Commercial Applications -- 12.2 Dimerization, Oligomerization, and Polymerization of Alkenes -- Catalyst Activation -- Microstructure -- Mechanism -- SHOP Oligomerization -- 12.3 Activation of CO And CO2 -- Water-Gas Shift -- Monsanto Acetic Acid Process -- CO2 Activation -- 12.4 C-H Activation -- Shilov Chemistry -- Other Routes -- C-C Bond Formation and Cleavage -- 12.5 Green Chemistry -- Alcohol Activation and Hydrogen Borrowing -- 12.6 Energy Chemistry -- References -- Problems -- 13: Clusters, Nanoparticles, Materials, and Surfaces -- 13.1 Cluster Structures -- Effective Atomic Number (EAN) Rule -- Wade-Mingos Rules -- 13.2 The Isolobal Analogy -- 13.3 Nanoparticles -- 13.4 Organometallic Materials -- Bulk Materials -- Porous Materials -- Metal Organic Frameworks (MOFs) -- Porous Organic Polymers (POPs) -- Organometallic Polymers -- Molecular Wires -- Molecular Electronics -- Nonlinear Optical (NLO) Materials -- Organic Light-Emitting Diodes (OLEDs) -- Sensors -- References -- Problems -- 14: Organic Applications -- 14.1 Carbon-Carbon Coupling -- 14.2 Metathesis -- 14.3 Cyclopropanation And C-H Insertion -- 14.4 Hydrogenation -- Kinetic Resolution -- Asymmetric Hydrogenation -- 14.5 Carbonylation -- 14.6 Oxidation -- 14.7 C-H Activation -- 14.8 Click Chemistry -- References -- Problems -- 15: Paramagnetic and High Oxidation-State Complexes -- 15.1 Magnetism and Spin States -- Spin States -- Influence of Spin State Changes on Kinetics and Thermodynamics -- 3d versus 4d and 5d Metals -- NMR Spectroscopy -- 15.2 Polyalkyls and Polyhydrides -- Group 4 -- Group 5 -- Group 6 -- Group 7 -- Groups 8-l0 -- Group 11.

Catalysis by High-Valent Oxo Complexes.